DFT Analysis of Organotin Catalytic Mechanisms in Dehydration Esterification Reactions for Terephthalic Acid and 2,2,4,4-Tetramethyl-1,3-cyclobutanediol.

Polyesters synthesized from 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) and terephthalic acid (TPA) are improved alternatives to toxic polycarbonates based on bisphenol A. In this work, we use ωB97X-D/LANL2DZdp calculations, in the presence of a benzaldehyde polarizable continuum model solvent, to show that esterification of TMCD and TPA will reduce and subsequently dehydrate a dimethyl tin oxide catalyst, becoming ligands on the now four-coordinate complex. This reaction then proceeds most plausibly by an intramolecular acyl-transfer mechanism from the tin complex, aided by a coordinated proton donor such as hydronium. These findings are a key first step in understanding polyester synthesis and avoiding undesirable side reactions during production.

Exploring the sensitivity in jellyfish locomotion under variations in scale, frequency, and duty cycle.

Jellyfish have been called one of the most energy-efficient animals in the world due to the ease in which they move through their fluid environment, by product of their bell kinematics coupled with their morphological, muscular, material properties. We investigated jellyfish locomotion by conducting in silico comparative studies and explored swimming performance across different fluid scales (i.e., Reynolds Number), bell contraction frequencies, and contraction phase kinematics (duty cycle) for a jellyfish with a fineness ratio of 1 (ratio of bell height to bell diameter). To study these relationships, an open source implementation of the immersed boundary method was used (IB2d) to solve the fully coupled fluid-structure interaction problem of a flexible jellyfish bell in a viscous fluid. Thorough 2D parameter subspace explorations illustrated optimal parameter combinations in which give rise to enhanced swimming performance. All performance metrics indicated a higher sensitivity to bell actuation frequency than fluid scale or duty cycle, via Sobol sensitivity analysis, on a higher performance parameter subspace. Moreover, Pareto-like fronts were identified in the overall performance space involving the cost of transport and forward swimming speed. Patterns emerged within these performance spaces when highlighting different parameter regions, which complemented the global sensitivity results. Lastly, an open source computational model for jellyfish locomotion is offered to the science community that can be used as a starting place for future numerical experimentation.

Dependence of deposition method on the molecular structure and stability of organosilanes revealed from degrafting by tetrabutylammonium fluoride.

We probe the structure of self-assembled monolayers (SAMs) comprising organosilanes deposited on flat silica-based surfaces prepared by liquid and vapor deposition by removing the organosilane molecules gradually from the underlying substrate via tetrabutylammonium fluoride (TBAF). Removal of organosilanes from the surface involves the cleavage of all pertinent Si-O bonds that anchor the organosilane molecules to the SAM, i.e., direct organosilane-surface linkages and in-plane crosslinks between neighboring organosilanes. We gain insight into the organosilane structure and stability by monitoring the organosilane density as a function of exposure time to TBAF. Degrafting of trifunctional chloro- and methoxy-alkylsilanes deposited from solution yields similar degrafting kinetics. We observe fast degrafting for organosilane SAMs deposited from the vapor phase, indicating that SAMs prepared in this manner form more loosely packed arrays, with less in-plane connectivity, compared to their solution-deposited counterparts. Bulkier, fluorinated silanes form more stable SAMs due to their ability to readily align and form a network with few aggregates and a relatively high fraction of surface bonds. The addition of a polymer brush to an anchored organosilane molecule demonstrates that increased bond tension accelerates the degrafting process despite the increased diffusion resistance.

Design and Fabrication of Wettability Gradients with Tunable Profiles through Degrafting Organosilane Layers from Silica Surfaces by Tetrabutylammonium Fluoride.

Surface-bound wettability gradients allow for a high-throughput approach to evaluate surface interactions for many biological and chemical processes. Here we describe the fabrication of surface wettability gradients on flat surfaces by a simple, two-step procedure that permits precise tuning of the gradient profile. This process involves the deposition of homogeneous silane SAMs followed by the formation of a surface coverage gradient through the selective removal of silanes from the substrate. Removal of silanes from the surface is achieved by using tetrabutylammonium fluoride which selectively cleaves the Si-O bonds at the headgroup of the silane. The kinetics of degrafting has been modeled by using a series of first order rate equations, based on the number of attachment points broken to remove a silane from the surface. Degrafting of monofunctional silanes exhibits a single exponential decay in surface coverage; however, there is a delay in degrafting of trifunctional silanes due to the presence of multiple attachment points. The effects of degrafting temperature and time are examined in detail and demonstrate the ability to reliably and precisely control the gradient profile on the surface. We observe a relatively homogeneous coverage of silane (i.e., without the presence of islands or holes) throughout the degrafting process, providing a much more uniform surface when compared to additive approaches of gradient formation. Linear gradients were formed on the substrates to demonstrate the reproducibility and tuneability of this subtractive approach.

The effect of a nurse manager's authentic leadership intervention on nurses' well-being: A single unit QI project.

INTRODUCTION: Nurse well-being is at the forefront of nursing leadership's focus, particularly with the impact of the ongoing COVID-19 pandemic. Nurse managers, as authentic leaders, should understand their role in supporting the spectrum of nurse well-being. At the negative end of well-being, leaders must address staff burnout as it increases nurse turnover, shortage of nurses, and poor patient outcomes. PURPOSE: The specific aim for this quality improvement (QI) project was to implement a program that could guide a nurse manager of a single inpatient unit on how to improve well-being in their nursing staff as measured by: (a) improved well-being scores to a composite score of 3.5 or greater as indicated by follow-up Culture Pulse surveys distributed in 2021; and (b) reduced absenteeism among nursing staff by 18%. RESULTS: Five surveys identical to the organization's work culture survey, that measures well-being, were sent to staff each month starting in January 2021 and ending in May 2021. The average composite score from all five surveys was 2.8, indicating an overall improvement. Absenteeism was reduced during implementation by 39%. DISCUSSION: This QI project guides nurse managers in the evidence-based interventions that can promote well-being in their staff.